Film-forming composition

ABSTRACT

A film-forming composition including a triazine ring-containing hyperbranched polymer with a repeating unit structure indicated by formula (1), and inorganic micro particles is provided. This enables the provision of a film-forming composition capable of hybridizing without reducing dispersion of the inorganic micro particles in a dispersion fluid, capable of depositing a coating film with a high refractive index, and suitable for electronic device film formation. 
                         
In the formula, R and R′ are mutually independent and indicate a hydrogen atom, an alkyl group, an alkoxy group, an aryl group, or an aralkyl group, and Ar indicates a divalent organic group including either an aromatic ring or a heterocyclic ring, or both.

CROSS REFERENCE TO RELATED APPLICATIONS

This application is a Divisional of application Ser. No. 13/818,546,filed on Feb. 22, 2013, now U.S. Pat. No. 9,243,165. Application Ser.No. 13/818,546 is the U.S. national phase of International ApplicationPCT/JP2011/068935, filed on Aug. 23, 2011. The benefit under 35 U.S.C.§119(a) is claimed to Japanese Patent Application No. 2010-187764, filedin Japan on Aug. 25, 2010. All of the foregoing applications are herebyexpressly incorporated by reference into the present application.

TECHNICAL FIELD

The present invention relates to a film-forming composition. Morespecifically, the invention relates to a film-forming composition whichincludes a triazine ring-containing hyperbranched polymer and inorganicfine particles.

BACKGROUND ART

Various efforts have hitherto been made to increase the functionality ofpolymeric compounds. For example, in one approach currently used toincrease the refractive index of polymeric compounds, aromatic rings,halogen atoms or sulfur atoms are introduced onto the compound. Of suchcompounds, episulfide polymeric compounds and thiourethane polymericcompounds, both of which have sulfur atoms introduced thereon, are inpractical use today as high-refractive index lenses for eyeglasses.

However, given that material design to a refractive index above 1.7 isdifficult with a polymer alone, the most effective method for achievingan even higher refractive index is known to involve the use of inorganicfine particles.

This method is a technique for achieving a higher refractive index bymixing together a polymer and inorganic fine particles. The mixingmethod generally entails mixing a polymer solution, with a dispersion ofinorganic fine particles, in which case the polymer serves as a binderwhich stabilizes and keeps the dispersion of inorganic fine particlesfrom breaking down.

It has been reported that polysiloxanes and polyimides can be used asthe binder polymer.

For example, a method for increasing the refractive index by using ahybrid material composed of a polysiloxane mixed with a materialcontaining a dispersed inorganic oxide such as zirconia or titania hasbeen disclosed (Patent Document 1).

A method for increasing the refractive index by using a hybrid materialcomposed of a polyimide mixed with an inorganic oxide or sulfidematerial containing dispersed titania, zinc sulfide or the like has alsobeen disclosed (Patent Document 2).

These hybrid materials have been modified in various ways to increasethe refractive index. However, when the refractive index of the binderpolymer and the refractive index of the inorganic fine particles arecompared, the refractive index of the inorganic fine particles isgenerally higher.

Hence, an effective way for increasing the refractive index of thehybrid material even further would be to increase the refractive indexof the lower refractive index component; i.e., the binder polymer.

This has led to the disclosure of, for example, a method for introducingcondensed ring structures having a high refractive index onto portionsof the polysiloxane (Patent Document 3), and a method for introducingsites that increase the electron density onto portions of the polyimide(Patent Document 4).

However, even in such binder polymers that have been modified toincrease the refractive index, the refractive index is currently about1.6 to 1.7, which is still lower than that of inorganic fine particles,which have refractive indices of about 1.8 to 2.1.

Hence, further increasing the refractive index of the binder polymer tomore than 1.7 is an important element for achieving a higher refractiveindex in hybrid materials.

In recent years, there has arisen a need for high-performance polymericmaterials in the development of electronic devices such asliquid-crystal displays, organic electroluminescent (EL) displays,optical semiconductor (LED) devices, solid-state image sensors, organicthin-film solar cells, dye-sensitized solar cells and organic thin-filmtransistors (TFT).

The specific properties desired in such polymeric materials include (1)heat resistance, (2) transparency, (3) high refractive index, (4) highsolubility, and (5) low volume shrinkage.

However, because the high refractive index lens materials for eyeglassesmentioned above generally have a poor heat resistance, requiring thatproduction be carried out in a temperature range no higher than 200° C.,materials of this type are unsuitable for processes such as baking inopen air at 300° C.

Moreover, because polymeric compounds in which aromatic rings ortriazine rings have been introduced generally have an inadequatesolubility in solvents, they are insoluble in resist solvents which aresafe solvents. On the other hand, materials which exhibit a highsolubility generally have a low transparency.

Although triazine ring-containing hyperbranched polymers synthesized aspolymers for use as flame retardants have been reported in theliterature (Non-Patent Document 1), there are no reports of suchhyperbranched polymers being hybridized with inorganic fine particles toform compositions.

As used herein, “hyperbranched polymer” refers to a highly branchedpolymer with an irregular branched structure that is obtained by, forexample, polymerizing ABx-type polyfunctional monomers (where A and Brepresent functional groups that react with each other, and “x” on B isa number equal to 2 or more). Highly branched polymers include also thepolymers having a regular branched structure that are referred to as“dendrimers.” However, hyperbranched polymers are characterized by beingeasier to synthesize than dendrimers, and by the ease with whichhigh-molecular-weight bodies can be synthesized.

PRIOR ART DOCUMENTS Patent Documents

-   Patent Document 1: JP-A 2007-246877-   Patent Document 2: JP-A 2001-354853-   Patent Document 3: JP-A 2008-24832-   Patent Document 4: JP-A 2008-169318

Non-Patent Documents

-   Non-Patent Document 1: Journal of Applied Polymer Science, 1006,    95-102 (2007)

SUMMARY OF THE INVENTION Problems to be Solved by the Invention

It is therefore an object of the present invention to provide afilm-forming composition that is highly suitable for the production offilms for electronic devices, which composition is capable ofhybridizing without reducing the dispersibility of inorganic fineparticles within a dispersion and moreover is able to form a highrefractive index film.

Means for Solving the Problems

The inventors earlier discovered that hyperbranched polymers containingrecurring units which include a triazine ring and an aromatic ring havea refractive index above 1.7, are able with the polymer alone to achievea high heat resistance, high transparency, high refractive index, highsolubility and low volume shrinkage, and are thus suitable asfilm-forming compositions in the fabrication of electronic devices(International Application PCT/JP 2010/057761).

Based on these findings, the inventors have conducted formerinvestigations and discovered that, by using such a hyperbranchedpolymer as a binder, because hybridization is possible withoutdecreasing the dispersibility of inorganic fine particles within adispersion and, moreover, a high refractive index is achieved,compositions containing such a polymer and inorganic fine particles arehighly suitable as film-forming compositions in the fabrication ofelectronic devices.

Accordingly, the invention provides:

1. A film-forming composition characterized by including a triazinering-containing hyperbranched polymer which includes recurring unitstructures of formula (1) below

(wherein R and R′ are each independently a hydrogen atom or an alkyl,alkoxy, aryl or aralkyl group; and Ar is a divalent organic group whichincludes either of, or both, an aromatic ring and a heterocycle), andinorganic fine particles.

2. The film-forming composition according to 1 above, wherein Ar is atleast one moiety selected from the group consisting of moieties offormulas (2) to (18) below

(wherein R¹ to R¹²⁸ are each independently a hydrogen atom, a halogenatom, a carboxyl group, a sulfonyl group, an alkyl group which may havea branched structure of 1 to 10 carbons, or an alkoxy group which mayhave a branched structure of 1 to 10 carbons; W¹ and W² are eachindependently a single bond, CR¹²⁹R¹³⁰ (R¹²⁹ and R¹³⁰ being eachindependently a hydrogen atom or an alkyl group which may have abranched structure of 1 to 10 carbons, with the proviso that R¹²⁹ andR¹³⁰ may together form a ring), C═O, O, S, SO, SO₂ or NR¹³¹ (R¹³¹ beinga hydrogen atom or an alkyl group which may have a branched structure of1 to 10 carbons); and X¹ and X² are each independently a single bond, analkylene group which may have a branched structure of 1 to 10 carbons,or a group of formula (19) below

(R¹³² to R¹³⁵ being each independently a hydrogen atom, a halogen atom,a carboxyl group, a sulfonyl group, an alkyl group which may have abranched structure of 1 to 10 carbons, or an alkoxy group which may havea branched structure of 1 to 10 carbons; and Y¹ and Y² being eachindependently a single bond or an alkylene group which may have abranched, structure of 1 to 10 carbons)).

3. The film-forming composition according to 2 above, wherein Ar is atleast one moiety selected from the group consisting of moieties offormulas (5) to (12) and moieties of formulas (14) to (18).

4. The film-forming composition according to 2 above, wherein Ar is atleast one moiety selected from the group consisting of moieties offormulas (20) to (22) below.

(wherein R³² to R³⁷, R⁶⁹ to R⁸⁰, R¹²⁹, R¹³⁰ and R¹³² to R¹³⁵ are asdefined above).

5. The film-forming composition according to 1 above, wherein therecurring unit-structure has formula (23) below.

6. The film-forming composition according to 1 above, wherein therecurring unit structure has formula (24) below

(wherein R and R′ are as defined above).

7. The film-forming composition according to 6 above, wherein therecurring unit structure has formula (25) below.

8. The film-forming composition according to any one of 1 to 7 above,wherein the hyperbranched polymer is capped on at least one end by analkyl, aralkyl, aryl, alkylamino, alkoxysilyl-containing alkylamino,aralkylamino, arylamino, alkoxy, aralkyloxy, aryloxy or ester group.

9. The film-forming composition according to 8 above, wherein thehyperbranched polymer has at least one terminal triazine ring which iscapped by an alkyl, aralkyl, aryl, alkylamino, alkoxysilyl-containingalkylamino, aralkylamino, arylamino, alkoxy, aralkyloxy, aryloxy orester group.

10. The film-forming composition according to any one of 1 to 9 above,wherein the inorganic fine particles are an oxide, sulfide or nitride ofone or more metal selected from the group consisting of Be, Al, Si, Ti,V, Fe, Cu, Zn, Y, Zr, Nb, Mo, In, Sn, Sb, Ta, W, Pb, Bi and Ce.

11. The film-forming composition according to 10 above, wherein theinorganic fine particles have a primary particle size of 2 to 50 nm andare colloidal particles of an oxide of one or more metal selected fromthe group consisting of Be, Al, Si, Ti, V, Fe, Cu, Zn, Y, Zr, Nb, Mo,In, Sn, Sb, Ta, W, Pb, Bi and Ce.

12. The film-forming composition according to 10 or 11 above, whereinthe inorganic fine particles are surface-treated with an organosiliconcompound.

13. A film obtained from the film-forming composition of any one of 1 to12 above.

14. An electronic device having a base material and the film of 13 aboveformed on the base material.

15. An optical member having a base material and the film of 13 aboveformed on the base material.

16. A solid-state image sensor formed of a charge-coupled device orcomplementary metal oxide semiconductor, which sensor has at least onelayer of the film of 13 above.

17. A solid-state image sensor having the film of claim 13 above as aplanarization layer on a color filter.

18. A lens material, planarizing material or embedding material for asolid-state image sensor, wherein the material includes the film-formingcomposition of any one of 1 to 12 above.

Advantageous Effect of the Invention

This invention, by using a triazine ring-containing hyperbranchedpolymer having, by itself, a refractive index of at least 1.7 as abinder polymer, is able to provide a film-forming composition which canachieve a high heat resistance, high transparency, high refractiveindex, high solubility and low volume shrinkage.

By employing the above polymer skeleton, a high heat resistance and ahigh transparency can be maintained even in cases where (1) a secondaryamine is used as a polymer spacer, and (2) a primary amine issubstituted at the chain ends. Hence, even in cases where monomer unitsthat were thought to invite a loss of beat resistance and transparencyare used, there is a possibility that the physical properties can becontrolled merely by changing the polymer skeleton to a hyperbranchedstructure.

The reason why the hyperbranched polymer used in this inventionmanifests a high refractive index is thought to be due to the fact that,because the polymer has a hyperbranched structure, the triazine ringsand aryl (Ar) moieties gather together closely, raising the electrondensity. In particular, it is thought that when R and/or R′ above arehydrogen, atoms, owing to me hyperbranched structure of the polymer, thenitrogen atoms on the triazine ring and the hydrogen atoms on the aminemoieties form hydrogen bonds, causing the triazine rings and aryl (Ar)moieties to cluster together even more closely and further increasingthe electron density.

Hence, even polymers which do not have sulfur atoms on the moleculeexhibit high refractive indices (as measured at a wavelength of 550 nm)of 1.70 or more.

The range in this refractive index varies also with the particularapplication, although the lower limit value is preferably at least 1.70,more preferably at least 1.75, and even more preferably at least 1.80.The upper limit value is typically not more than about 2.00 to 1.95.

Also, even in cases where a rigid moiety such as a fluorene skeleton isused in the main recurring units of the polymer, a varnish that uses aresist solvent having a high safety can be prepared without a loss ofsolubility.

Furthermore, polymers which, in spite of being high-molecular-weightcompounds, are of low viscosity when dissolved in a solvent and moreovercontain m-phenylenediamine moieties have an excellent solubility,particularly in various types of organic solvents, and thus have anexcellent handleability.

The physical properties possessed by the triazine ring-containinghyperbranched polymer used in the invention can be controlled bychanging the types of monomers serving as the starting material duringsynthesis.

Films produced using the inventive film-forming composition whichincludes a triazine ring-containing hyperbranched polymer and inorganicfine particles and has characteristics such as the above can beadvantageously used as components in the fabrication of electronicdevices such as liquid-crystal displays, organic electroluminescent (EL)displays, optical semiconductor (LED) devices, solid-state imagesensors, organic thin-film solar cells, dye-sensitized solar cells andorganic thin-film transistors (TFT). Such films can also beadvantageously used as lens components which are required to have a highrefractive index. In particular, such films can be advantageously usedas the following solid-state image sensor components which are requiredto have especially high refractive indices: embedding films andplanarizing films on photodiodes, planarizing films before and aftercolor filters, microlenses, planarizing films on microlenses, andconformal films.

BRIEF DESCRIPTION OF DRAWINGS

FIG. 1 is an ¹H-NMR spectrum of the hyperbranched polymer [3] obtainedin Synthesis Example 1.

FIG. 2 is a plot showing the transmittance of the film produced inExample 1.

FIG. 3 is a plot showing the transmittance of the film produced inExample 2.

FIG. 4 is a plot showing the transmittance of the film produced inExample 3.

FIG. 5 is a plot showing the transmittance of the film produced inExample 4.

FIG. 6 is a plot showing the transmittance of the film produced inExample 5.

FIG. 7 is a plot showing the transmittance of the film produced inExample 6.

FIG. 8 is a plot showing the transmittance of the film produced inExample 7.

FIG. 9 is a plot showing the transmittance of the film produced inExample 8.

FIG. 10 is a plot showing the transmittance of the film produced inExample 9.

FIG. 11 is a plot showing the transmittance of the film produced inComparative Example 1.

FIG. 12 is a plot showing the transmittance of the film produced inComparative Example 2.

FIG. 13 is a plot showing the transmittance of the film produced inComparative Example 3.

EMBODIMENT FOR CARRYING OUT THE INVENTION

The invention is described more fully below.

The film-forming composition according to the present invention includesa hyperbranched polymer containing recurring unit structures of formula(1) below and inorganic fine particles.

In the above formula, R and R′ are each independently a hydrogen atom oran alkyl, alkoxy, aryl or aralkyl group.

In the invention, the number of carbons on the alkyl group, although notparticularly limited, is preferably from 1 to 20. From the standpoint offurther increasing the heat resistance of the polymer, the number ofcarbons is more preferably from 1 to 10, and even more preferably from 1to 3. The alkyl group may have a linear, branched or cyclic structure.

Illustrative examples of alkyl groups include methyl, ethyl, n-propyl,isopropyl, cyclopropyl, n-butyl, isobutyl, s-butyl, t-butyl, cyclobutyl,1-methylcyclopropyl, 2-methylcyclopropyl, n-pentyl, 1-methyl-n-butyl,2-methyl-n-butyl, 3-methyl-n-butyl, 1,1-dimethyl-n-propyl,1,2-dimethyl-n-propyl, 2,2-dimethyl-n-propyl, 1-ethyl-n-propyl,cyclopentyl, 1-methylcyclobutyl, 2-methylcyclobutyl, 3-methylcyclobutyl,1,2-dimethylcyclopropyl, 2,3-dimethylcyclopropyl, 1-ethylcyclopropyl,2-ethylcyclopropyl, n-hexyl, 1-methyl-n-pentyl, 2-methyl-n-pentyl,3-methyl-n-pentyl, 4-methyl-n-pentyl, 1,1-dimethyl-n-butyl,1,2-dimethyl-n-butyl, 1,3-dimethyl-n-butyl, 2,2-dimethyl-n-butyl,2,3-dimethyl-n-butyl, 3,3-dimethyl-n-butyl, 1-ethyl-n-butyl,2-ethyl-n-butyl, 1,1,2-trimethyl-n-propyl, 1,2,2-trimethyl-n-propyl,1-ethyl-1-methyl-n-propyl, 1-ethyl-2-methyl-n-propyl, cyclohexyl,1-methylcyclopentyl, 2-methylcyclopentyl, 3-methylcyclopentyl,1-ethylcyclobutyl, 2-ethylcyclobutyl, 3-ethylcyclobutyl,1,2-dimethylcyclobutyl, 1,3-dimethylcyclobutyl, 2,2-dimethylcyclobutyl,2,3-dimethylcyclobutyl, 2,4-dimethylcyclobutyl, 3,3-dimethylcyclobutyl,1-n-propylcyclopropyl, 2-n-propylcyclopropyl, 1-isopropylcyclopropyl,2-isopropylcyclopropyl, 1,2,2-trimethylcyclopropyl,1,2,3-trimethylcyclopropyl, 2,2,3-trimethylcyclopropyl,1-ethyl-2-methylcyclopropyl, 2-ethyl-1-methylcyclopropyl,2-ethyl-2-methylcyclopropyl and 2-ethyl-3-methylcyclopropyl.

The number of carbons on the alkoxy group, although not particularlylimited, is preferably from 1 to 20. From the standpoint of furtherincreasing the heat resistance of the polymer, the number of carbons ismore preferably from 1 to 10, and even more preferably from 1 to 3. Thealkyl moiety thereon may have a linear, branched or cyclic structure.

Illustrative examples of alkoxy groups include methoxy, ethoxy,n-propoxy, isopropoxy, n-butoxy, isobutoxy, s-butoxy, t-butoxy,n-pentoxy, 1-methyl-n-butoxy, 2-methyl-n-butoxy, 3-methyl-n-butoxy,1,1-dimethyl-n-propoxy, 1,2-dimethyl-n-propoxy, 2,2-dimethyl-n-propoxy,1-ethyl-n-propoxy, n-hexyloxy, 1-methyl-n-pentyloxy,2-methyl-n-pentyloxy, 3-methyl-n-pentyloxy, 4-methyl-n-pentyloxy,1,1-dimethyl-n-butoxy, 1,2-dimethyl-n-butoxy, 1,3-dimethyl-n-butoxy,2,2-dimethyl-n-butoxy, 2,3-dimethyl-n-butoxy, 3,3-dimethyl-n-butoxy,1-ethyl-n-butoxy, 2-ethyl-n-butoxy, 1,1,2-trimethyl-n-propoxy,1,2,2-trimethyl-n-propoxy, 1-ethyl-1-methyl-n-propoxy and1-ethyl-2-methyl-n-propoxy.

The number of carbons on the aryl group, although not particularlylimited, is preferably from 6 to 40. From the standpoint of furtherincreasing the heat resistance of the polymer, the number of carbons ismore preferably from 6 to 16, and even more preferably from 6 to 13.

Illustrative examples of aryl groups include phenyl, o-chlorophenyl,m-chlorophenyl, p-chlorophenyl, o-fluorophenyl, p-fluorophenyl,o-methoxyphenyl, p-methoxyphenyl, p-nitrophenyl, p-cyanophenyl,α-naphthyl, β-naphthyl, o-biphenylyl, m-biphenylyl, p-biphenylyl,1-anthryl, 2-anthryl, 9-anthryl, 1-phenanthryl, 2-phenanthryl,3-phenanthryl, 4-phenanthryl and 9-phenanthryl.

The number of carbons on the aralkyl group, although not particularlylimited, is preferably from 7 to 20. The alkyl moiety thereon may belinear, branched or cyclic.

Illustrative examples of aralkyl groups include benzyl,p-methylphenylmethyl, m-methylphenylmethyl, o-ethylphenylmethyl,m-ethylphenylmethyl, p-ethylphenylmethyl, 2-propylphenylmethyl,4-isopropylphenylmethyl, 4-isobutylphenylmethyl and α-naphtylmethyl.

In above formula (1), Ar is a divalent organic group which includeseither of, or both, an aromatic ring and a heterocycle, and is nototherwise limited. In the present invention, Ar is preferably at leastone moiety from among those of formulas (2) to (18) below, morepreferably at least one moiety from among those of formulas (5) to (18),and even more preferably at least one moiety from among those offormulas (5), (7), (8), (11), (12) and (14) to (18).

In the above formulas, R¹ to R¹²⁸ are each independently a hydrogenatom, a halogen atom, a carboxyl group, a sulfonyl group, an alkyl groupwhich may have a branched structure of 1 to 10 carbons, or an alkoxygroup which may have a branched structure of 1 to 10 carbons. W¹ and W²are each independently a single bond, CR¹²⁹R¹³⁰ (wherein R¹²⁹ and R¹³⁰are each independently a hydrogen atom or an alkyl group which may havea branched structure of 1 to 10 carbons, with the proviso that R¹²⁹ andR¹³⁰ may together form a ring), C═O, O, S, SO, SO₂ or NR¹³¹ (whereinR¹³¹ is a hydrogen atom or an alkyl group which may have a branchedstructure of 1 to 10 carbons).

These alkyl groups and alkoxy groups are exemplified by the same groupsas mentioned above.

Examples of the halogen atom include fluorine, chlorine, bromine andiodine.

X¹ and X² are each independently a single bond, an alkylene group whichmay have a branched structure of 1 to 10 carbons, or a group of formula(19) below.

In the above formula, R¹³² to R¹³⁵ are each independently a hydrogenatom, a halogen atom, a carboxyl group, a sulfonyl group, an alkyl groupwhich may have a branched structure of 1 to 10 carbons, or an alkoxystructure which may have a branched structure of 1 to 10 carbons. Y¹ andY² are each independently a single bond or an alkylene group which mayhave a branched structure of 1 to 10 carbons.

These halogen atoms, alkyl groups and alkoxy groups are exemplified bythe same groups as mentioned above.

Illustrative examples of the alkylene group which may have a branchedstructure of 1 To 10 carbons include methylene, ethylene, propylene,trimethylene, tetramethylene and pentamethylene.

Preferred examples of Ar in the present invention include divalentorganic groups having a fluorene ring. For example, divalent organicgroups of formulas (20) and (21) below are preferred.

In the above formulas, R³² to R³⁷, R⁶⁹ to R⁷⁶, R¹²⁹, R¹³⁰ and R¹³² toR¹³⁵ are each as defined above, although all are preferably hydrogenatoms.

Illustrative examples of the aryl groups of above formulas (2) to (18)include, but are not limited to, the following.

Of these, to obtain a polymer having a higher refractive index, the arylgroups of the following formulas are more preferred.

Moreover, from the standpoint of achieving a high refractive index, anaryl (Ar) moiety with a rigid structure having a cyclic skeleton such asa fluorene skeleton or a carbazole skeleton is preferable because thearyl (Ar) moieties tend to cluster together, increasing the electrondensity. Alternatively, a simple benzene ring is also preferablebecause, being small structures, aryl (Ar) moieties tend to clustertogether, increasing the electron density.

As for benzene ring linkages such as W¹, functional groups having a highhydrogen bonding ability, such as carbonyl containing groups and aminesare preferred because these form hydrogen bonds with hydrogen atoms onamine moieties (in cases where R and/or R′ are hydrogen atoms), as aresult of which the aryl (Ar) moieties tend to cluster together,increasing the electron density.

From the above standpoint, aryl groups of the following formulas arepreferred.

To achieve an even higher refractive index, aryl groups of the followingformulas are more preferred.

Examples of preferred recurring unit structures include, but are notlimited to, those of formula (23) below.

to further increase the solubility of the hyperbranched polymer inhighly safe solvents such as resist solvents, an m-phenylenediaminederivative group of formula (22) below is preferred as the Ar group.

In the above formula, R⁷⁷ to R⁸⁰ are as defined above, although all arepreferably hydrogen atoms.

Therefore, preferred recurring unit structures which give the polymer agood solubility include those of formula (24) below. In particular,hyperbranched polymers having recurring unit structures of formula (25)below in which R and R′ are both hydrogen atoms are best.

In the above formula, R and R′ are as defined above.

The hyperbranched polymer used in the present invention has aweight-average molecular weight which, although not particularlylimited, is preferably between 500 and 500,000, and more preferablybetween 500 and 100,000. To further enhance the heat resistance andlower the shrinkage ratio, the weight-average molecular weight ispreferably at least 2,000. To further increase the solubility and lowerthe viscosity of the resulting solution, the weight-average molecularweight is preferably 50,000 or less, more preferably 30,000 or less, andeven more preferably 10,000 or less.

The weight-average molecular weight in the invention is theweight-average molecular weight measured by gel permeationchromatography (GPC) against a polystyrene standard.

Exemplary methods for preparing the triazine ring-containinghyperbranched polymer used in the invention are described. Thepreparation methods are divided up below into Schemes 1, 2 and 3, eachof which is further divided into “a”, “b,” etc.

For example, as shown in Scheme 1-a below, a hyperbranched polymerhaving the recurring structure (23′) can be obtained by reacting acyanuric halide (26) with an amino group-bearing bisaminophenylfluorenecompound (27) in a suitable organic solvent.

As shown in Scheme 1-b below, a hyperbranched polymer having therecurring structure (24′) can be obtained by reacting a cyanuric halide(26) with an m-phenylenediamine compound (28) in a suitable organicsolvent.

In the above formulas, each occurrence of X is independently a halogenatom; and R is as defined above.

Alternatively, as shown in Scheme 2-a below, a hyperbranched polymerhaving the recurring structure (23′) can be synthesized from a compound(29) obtained by reacting equimolar amounts of a cyanuric halide (26)and an amino group-bearing bisaminophenylfluorene compound (27) in asuitable organic solvent.

As shown in Scheme 2-b below, a hyperbranched polymer having therecurring structure (24′) can be synthesized from a compound (30)obtained by reacting equimolar amounts of a cyanuric halide (26) and anm-phenylenediamine compound (28) in a suitable organic solvent.

In the above formulas, each occurrence of X is independently a halogenatom; and R is as defined above.

By using the above methods, the hyperbranched polymer of the inventioncan be easily and safely produced at a low cost. Because the reactiontime in these methods is much shorter than in the synthesis of ordinarypolymers, these production methods are compatible with recent concernsfor the environment and are capable of reducing CO₂ emissions. Moreover,such methods can carry out stable production even when the scale ofproduction is greatly expanded, and thus allow a stable supply system tobe maintained even at an industrial level.

In particular, taking into account the stability of cyanuric chloride asa starting material and also from an industrial perspective, theproduction methods of Scheme 2 are more preferred.

In the methods of Schemes 1 and 2, the respective starting materials maybe charged in any suitable amounts so long as the target hyperbranchedpolymer is obtained, although the use of from 0.01 to 10 equivalents ofthe diamines compound (27), (28) per equivalent of the cyanuric halide(26) is preferred.

In the method of Scheme 1 in particular, it is preferable to avoid using3 equivalents of the diamino compound (27), (28) per 2 equivalents ofthe cyanuric halide (26). By having the number of equivalents of therespective functional groups differ from this ratio, the formation of agel can be prevented.

To obtain hyperbranched polymers of various molecular weights which havemany terminal triazine rings, it is preferable to use the diaminocompound (27), (28) in an amount of less than 3 equivalents per 2equivalents of the cyanuric halide (26).

On the other hand, to obtain hyperbranched polymers of various molecularweights which have many terminal amines, it is preferable to use thecyanuric halide (26) in an amount of less than 2 equivalents per 3equivalents of the diamino compound (27), (28).

For example, in cases where a thin film has been produced, in order forthe film to have an excellent transparency and light resistance, ahyperbranched polymer having many terminal triazine rings is preferred.

By suitably regulating the amounts of the diamino compound (27), (28)and the cyanuric halide (26) in this way, the molecular weight of theresulting hyperbranched polymer can easily be regulated.

Various solvents that are commonly used in this type of reaction may beused as the organic solvent. Illustrative examples includetetrahydrofuran, dioxane, dimethylsulfoxide; amide solvents such asN,N-dimethylformamide, N-methyl-2-pyrrolidone, tetramethylurea,hexamethylphosphoramide, N,N-dimethylacetamide, N-methyl-2-piperidone,N,N-dimethylethyleneurea, N,N,N′,N′-tetramethylmalonamide,N-methylcaprolactam, N-acetylpyrrolidine, N,N-diethylacetamide,N-ethyl-2-pyrrolidone, N,N-dimethylpropionamide,N,N-dimethylisobutyramide, N-methylformamide andN,N′-dimethylpropyleneurea; and mixed solvents thereof.

Of the above, N,N-dimethylformamide, dimethylsulfoxide,N-methyl-2-pyrrolidone, N,N-dimethylacetamide and mixed solvents thereofare preferred. N,N-Dimethylacetamide and N-methyl-2-pyrrolidone areespecially preferred.

In the Scheme 1 reaction and the second stage reaction in Scheme 2, thereaction temperature may be suitably set in the range from the meltingpoint of the solvent used to the boiling point of the solvent, althoughthe temperature is preferably from about 0° C. to about 150° C., andmore preferably from 60 to 100° C.

In the Scheme 1 reaction in particular, to suppress linearity andincrease the degree of branching, the reaction temperature is preferablyfrom 60 to 150° C., more preferably from 80 to 150° C., and even morepreferably from 80 to 120° C.

In the first stage reaction of Scheme 2, the reaction temperature may besuitably set in the range from the melting point of the solvent used tothe boiling point of the solvent, with a temperature of from about −50to about 50° C. being preferred, a temperature of from about −20 toabout 50° C. being more preferred, a temperature of from about −10 toabout 50° C. being even more preferred, and a temperature of from −10 to10° C. being still more preferred.

In the Scheme 2 method in particular, the use of a two-stage processwith a first step involving reaction at from −50 to 50° C., followed bya second step involving reaction at from 60 to 150° C. is preferred.

In each of the above reactions, the ingredients may be added in anyorder. However, in the Scheme 1 reaction, the best method is to heat asolution containing either the cyanuric halide (26) or the diaminecompound (27), (28) and the organic solvent to a temperature of from 60to 150° C., and preferably from 80 to 150° C., then add the remainingingredient—the diamine compound (27), (28) or the cyanuric halide(26)—to the resulting solution, at this temperature.

In this case, either ingredient may be used as the ingredient which isinitially dissolved in the solvent or as the ingredient which issubsequently added, although a method wherein the cyanuric halide (26)is added to a heated solution of the diamine compound (27), (28) ispreferred.

In the Scheme 2 reactions, either ingredient may be used as theingredient which is initially dissolved in the solvent or as theingredient which is subsequently added, although a method wherein thediamine compound (27), (28) is added to a cooled solution of thecyanuric halide (26) is preferred.

The subsequently added ingredient may be added neat or may be added as asolution of the ingredient dissolved in an organic solvent such as anyof those mentioned above. However, taking into account the ease of theoperations and the controllability of the reaction, the latter approachis preferred.

Also, addition may be carried out gradually such as in a dropwisemanner, or the entire amount may be added all at once in a batchwisemanner.

In Scheme 1, even in cases where the reaction is carried out in a singlestage (without raising the temperature in a stepwise fashion), in aheated state and after both, compounds have been mixed, the desiredtriazine ring-containing hyperbranched polymer can be obtained withoutgelation.

In the Scheme 1 reaction and the second stage reaction in Scheme 2,various bases which are commonly used during or after polymerization maybe added.

Illustrative examples of such bases include potassium carbonate,potassium hydroxide, sodium carbonate, sodium hydroxide, sodiumbicarbonate, sodium ethoxide, sodium acetate, lithium carbonate, lithiumhydroxide, lithium oxide, potassium acetate, magnesium oxide, calciumoxide, barium hydroxide, trilithium phosphate, trisodium phosphate,tripotassium phosphate, cesium fluoride, aluminum oxide, ammonia,trimethylamine, triethylamine, diisopropylmethylamine,diisopropylethylamine, N-methylpiperidine,2,2,6,6-tetramethyl-N-methylpiperidine, pyridine,4-dimethylaminopyridine and N-methylmorpholine.

The amount of base added per equivalent of the cyanuric halide (26) ispreferably from 1 to 100 equivalents, and more preferably from 1 to 10equivalents. These bases may also be used in the form of an aqueoussolution.

Although it is preferable for no starting ingredients to remain in theresulting polymer, some starting material may remain, provided this doesnot interfere with the advantageous effects of the invention.

In the methods of both schemes, following reaction completion, theproduct can be easily purified by a suitable technique such asreprecipitation.

Also, in the present invention, some portion of the halogen atoms on atleast one terminal triazine ring may be capped by, for example, an alkylaralkyl, aryl, alkylamino, alkoxysilyl-containing alkylamino,aralkylamino, arylamino, alkoxy, aralkyloxy, aryloxy or ester group.

Of these, alkylamino, alkoxysilyl-containing alkylamino, aralkylaminoand arylamino groups are preferred. Alkylamino and arylamino groups aremore preferred. An arylamino group is even more preferred.

Illustrative examples of ester groups include methoxycarbonyl andethoxycarbonyl.

Illustrative examples of alkylamino groups include methylamino,ethylamino, n-propylamino, isopropylamino, n-butylamino, isobutylamino,s-butylamino, t-butylamino, n-pentylamino, 1-methyl-n-butylamino,2-methyl-n-butylamino, 3-methyl-n-butylamino,1,1-dimethyl-n-propylamino, 1,2-dimethyl-n-propylamino,2,2-dimethyl-n-propylamino, 1-ethyl-n-propylamino, n-hexylamino,1-methyl-n-pentylamino, 2-methyl-n-pentylamino, 3-methyl-n-pentylamino,4-methyl-n-pentylamino, 1,1-dimethyl-n-butylamino,1,2-dimethyl-n-butylamino, 1,3-dimethyl-n-butylamino,2,2-dimethyl-n-butylamino, 2,3-dimethyl-n-butylamino,3,3-dimethyl-n-butylamino, 1-ethyl-n-butylamino, 2-ethyl-n-butylamino,1,1,2-trimethyl-n-propylamino, 1,2,2-trimethyl-n-propylamino,1-ethyl-1-methyl-n-propylamino and 1-ethyl-2-methyl-n-propylamino.

Illustrative examples of aralkylamino groups include benzylamino,methoxycarbonylphenylmethylamino, ethoxycarbonylphenylmethylamino,p-methylphenylmethylamino, m-methylphenylmethylamino,o-ethylphenylmethylamino, m-ethylphenylmethylamino,p-ethylphenylmethylamino, 2-propylphenylmethylamino,4-isopropylphenylmethylamino, 4-isobutylphenylmethylamino,naphthylmethylamino, methoxycarbonylnaphthylmethylamino andethoxycarbonylnaphthylmethylamino.

Illustrative examples of arylamino groups include phenylamino,methoxycarbonylphenylamino, ethoxycarbonylphenylamino, naphthylamino,methoxycarbonylnaphthylamino, ethoxycarbonynaphthylamino,anthranylamino, pyrenylamino, biphenylamino, terphenylamino andfluorenylamino.

Alkoxysilyl-containing alkylamino groups are exemplified bymonoalkoxysilyl-containing alkylamino groups, dialkoxysilyl-containingalkylamino groups and trialkoxysilyl-containing alkylamino groups.Illustrative examples include 3-trimethoxysilylpropylamino,3-triethoxysilylpropylamino, 3-dimethylethoxysilylpropylamino,3-methyldiethoxysilylpropylamino,N-(2-aminoethyl)-3-dimethylmethoxysilylpropylamino,N-(2-aminoethyl)-3-methyldimethoxysilylpropylamino andN-(2-aminoethyl)-3-trimethoxysilylpropylamino.

Illustrative examples of aryloxy groups include phenoxy, naphthoxy,anthranyloxy, pyrenyloxy, biphenyloxy, terphenyloxy and fluorenyloxy.

Illustrative examples of aralkyloxy groups include benzyloxy,p-methylphenylmethyloxy, m-methylphenylmethyloxy,o-ethylphenylmethyloxy, m-ethylphenylmethyloxy, p-ethylphenylmethyloxy,2-propylphenylmethyloxy, 4-isopropylphenylmethyloxy,4-isobutylphenylmethyloxy and α-naphthylmethyloxy.

Alkyl groups, aralkyl groups, aryl groups and alkoxy groups areexemplified in the same way as described earlier in the specification.

These groups can be easily introduced by substituting a halogen atom ona triazine ring with a compound that furnishes the correspondingsubstituent. For example, as shown in Schemes 3-a and 3-b below, byadding an aniline derivative and inducing a reaction, hyperbranchedpolymers (31), (32) having a phenylamino group on at least one chain endare obtained.

In these formulas, X and R are as defined above.

At this time, by reacting the cyanuric halide with a diaminoarylcompound while concurrently charging an organic monoamine, i.e., in thepresence of an organic monoamine, it is possible to obtain a flexiblehyperbranched polymer having a low degree of branching in which therigidity of the hyperbranched polymer has been mitigated.

Because the hyperbranched polymer obtained in this way has an excellentsolubility in a solvent (meaning that aggregation is inhibited) and hasan excellent crosslinkability with a crosslinking agent, it isespecially advantageous when used as a composition in combination withthe subsequently described crosslinking agent.

An alkyl monoamine, aralkyl monoamine or aryl monoamine may be used hereas the organic monoamine.

Illustrative examples of alkyl monoamines include methylamine,ethylamine, n-propylamine, isopropylamine, n-butylamine, isobutylamine,s-butylamine, t-butylamine, n-pentylamine, 1-methyl-n-butylamine,2-methyl-n-butylamine, 3-methyl-n-butylamine,1,1-dimethyl-n-propylamine, 1,2-dimethyl-n-propylamine,2,2-dimethyl-n-propylamine, 1-ethyl-n-propylamine, n-hexylamine,1-methyl-n-pentylamine, 2-methyl-n-pentylamine, 3-methyl-n-pentylamine,4-methyl-n-pentylamine, 1,1-dimethyl-n-butylamine,1,2-dimethyl-n-butylamine, 1,3-dimethyl-n-butylamine,2,2-dimethyl-n-butylamine, 2,3-dimethyl-n-butylamine,3,3-dimethyl-n-butylamine, 1-ethyl-n-butylamine, 2-ethyl-n-butylamine,1,1,2-trimethyl-n-propylamine, 1,2,2-trimethyl-n-propylamine,1-ethyl-1-methyl-n-propylamine, 1-ethyl-2-methyl-n-propylamine and2-ethylhexylamine.

Illustrative examples of aralkyl monoamines include benzylamine,p-methoxycarbonylbenzylamine, p-ethoxycarbonylbenzylamine,p-methylbenzylamine, m-methylbenzylamine and o-methoxybenzylamine.

Illustrative examples of aryl monoamines include aniline,p-methoxycarbonylaniline, p-ethoxycarbonylaniline, p-methoxyaniline,1-naphthylamine, 2-naphthylamine, anthranylamine, 1-aminopyrene,4-biphenylylamine, o-phenylaniline, 4-amino-p-terphenyl and2-aminofluorene.

In this case, the amount of organic monoamine used per equivalent of thecyanuric halide is set to preferably from 0.05 to 500 equivalents, morepreferably from 0.05 to 120 equivalents, and even more preferably from0.05 to 50 equivalents.

To suppress linearity and increase the degree of branching, the reactiontemperature in this case is preferably from 60 to 150° C., morepreferably from 80 to 150° C., and even more preferably from 80 to 120°C.

However, mixing of the three ingredients—an organic monoamine, acyanuric halide and a diaminoaryl compound—may be carried out at a lowtemperature, in which case the temperature is set to preferably fromabout −50° C. to about 50° C., more preferably from about −20° C. toabout 50° C., and even more preferably from about −20° C. to about 10°C. Following low-temperature charging, it is preferable to raise thetemperature without interruption (in a single step) to thepolymerization temperature and carry out the reaction.

Alternatively, the mixing of two ingredients—a cyanuric halide and adiaminoaryl Compound—may be carried out at a low temperature, in whichcase the temperature is set to preferably from about −50° C. to about50° C., more preferably from about −20° C. to about 50° C., and evenmore preferably from about −20° C. to about 10° C. Followinglow-temperature charging, it is preferable to raise the temperaturewithout interruption (in a single step) to the polymerizationtemperature and carry out the reaction.

The reaction of the cyanotic halide with the diaminoaryl compound in thepresence of such an organic monoamine may be carried out using anorganic solvent like those mentioned above.

The inorganic fine particles which, together with the above-describedhyperbranched polymer, make up the inventive composition are not subjectto any particular limitation. However, in this invention, an oxide,sulfide or nitride of one or more metal selected from the groupconsisting of Be, Al, Si, Ti, V, Fe, Cu, Zn, Y, Zr, Nb, Mo, In, Sn, Sb,Ta, W, Pb, Bi and Ce is preferred. Oxides of these metals are especiallypreferred.

A single type of inorganic fine particle may be used alone or two ormore types may be used in combination.

Illustrative examples of metal oxides include Al₂O₃, ZnO, TiO₂, ZrO₂,Fe₂O₃, Sb₂O₅, BeO, ZnO, SnO₂, CeO₂, SiO₂ and WO₃.

Using a plurality of metal oxides as a complex oxide is also effective.As used herein, “complex oxide” refers to two or more inorganic oxideswhich have been mixed together in the fine particle production stage.Illustrative examples include complex oxides of TiO₂ with ZrO₂, of TiO₂with ZrO₂ and SnO₂, and of ZrO₂ with SnO₂.

The metal oxide may also be a compound of two or more of the abovemetals, such as ZnSb₂O₆, BaTiO₃, SrTiO₃ and SrSnO₃. Such compounds maybe used singly, or two or more may be used in admixture. Moreover, suchcompounds may be used in admixture with the above oxides.

No particular limitation is imposed on the size of the inorganic fineparticles. However, to further increase their dispersibility in adispersion, the particles have a primary particle size of preferablyfrom 2 to 50 mm, and more preferably from 5 to 15 mm. The primaryparticle size is the value obtained by examination with a transmissionelectron microscope.

When the above inorganic fine particles are used, the particles may beused directly as is, or may be used in a colloidal state obtained byfirst dispersing the fine particles in water or an organic solvent(i.e., colloidal particles).

In addition, the inorganic fine particles used may be fine particlesthat have been treated with, for example, silicon oxide, anorganosilicon compound or an organometallic compound.

“Treatment with silicon oxide” refers to growing fine particles ofsilicon oxide by a known process on the surface of the particles withinan inorganic fine particle-containing dispersion, “Treatment with anorganosilicon compound or an organometallic compound” refers to addingthese compounds to an inorganic fine particle-containing dispersion,then stirring under applied heat.

The organosilicon compound is exemplified by silane coupling agents andsilanes. Illustrative examples of silane coupling agents includevinyltrichlorosilane, vinyltrimethoxysilane, vinyltriethoxysilane,2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane,3-glycidoxypropyltrimethoxysilane,3-glycidoxypropylmethylditriethoxysilane,3-glycidoxypropyltriethoxysilane, p-styryltrimethoxysilane,3-methacryloxypropylmethyldimethoxysilane,3-methacryloxypropyltrimethoxysilane,3-methacryloxypropylmethyldiethoxysilane,3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane,N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane,N-2-(aminoethyl)-3-aminopropylmethyltrimethoxysilane,N-2-(aminoethyl)-3-aminopropylmethyltriethoxysilane,3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane,3-trimethoxysilyl-N-(1,3-dimethylbutylidene)propylamine,N-phenyl-3-aminopropyltrimethoxysilane, 3-chloropropyltrimethoxysilane,3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane,bis(triethoxysilylpropyl)tetrasulfide and3-isocyanatopropyltriethoxysilane.

Illustrative examples of silanes include methyltrichlorosilane,dimethyldichlorosilane, trimethylchlorosilane, phenyltrichorosilane,methyltrimethoxysilane, dimethyldimethoxysilane, phenyltrimethoxysilane,methyltriethoxysilane, methyltriethoxysilane, dimethyldiethoxysilane,phenyltriethoxysilane, n-propyltrimethoxysilane,n-propyltriethoxysilane, hexyltrimethoxysilane, hexyltriethoxysilane,decyltrimethoxysilane, trifluoropropyltrimethoxysilane andhexamethyldisilazane.

The organometallic compound is exemplified by titanate coupling agentsand aluminum coupling agents. Illustrative examples of titanate couplingagents include Plenact KR TTS, KR 46B, KR 38B, KR I38S, KR 238S, KR338X, KR 44, KR 9SA, KR ET5 and KR ET (front Ajinomoto Fine-Techno Co.,Inc.). Illustrative examples of aluminum coupling agents include PlenactAL-M (Ajinomoto Fine-Techno Co., Inc.).

These organosilicon compounds and organometallic compounds are used inan amount of preferably from 2 to 100 parts by weight per 100 parts byweight of the inorganic fine particles.

Metal oxide colloidal particles can be produced by a known method, suchas an ion-exchange process, a peptization process, a hydrolysis processor a reaction process.

Ion-exchange processes are exemplified by methods involving thetreatment of acidic salts of the above metals with a hydrogenion-exchange resin, and methods involving the treatment of basic saltsof the above metals with a hydroxyl anion-exchange resin.

Peptization processes are exemplified by methods that involveneutralizing acidic salts of the above metals with a base, methods thatinvolve hydrolyzing alkoxides of the above metals, and methods thatinvolve hydrolyzing basic salts of the above metals under heating, thenremoving unnecessary acid.

Reaction methods are exemplified by methods that involve reactingpowders of the above metals with an acid.

The inventive film-forming composition which includes a triazinering-containing hyperbranched polymer and inorganic fine particles ispreferably a varnish obtained by the hybridization of these respectiveingredients, which varnish is a uniform dispersion.

As used herein, “hybridization” refers broadly to mixing togethersolutes of differing character and having them intermingle in the stateof a solution. So long as their dispersibilities are maintained, thediffering solutes may or may not chemically or physically interact.

The method of hybridization is not subject to any particular limitation,provided stability is achieved in the final varnish.

Examples of methods of hybridization include: (1) mixing the triazinering-containing hyperbranched polymer in a solid state into a dispersionof the inorganic fine particles, (2) mixing a solution of the triazinering-containing hyperbranched polymer into a dispersion of the inorganicfine particles, and (3) adding the triazine ring-containinghyperbranched polymer in a solid state at the same time as an inorganicfine particle dispersing step to form a dispersion. From the standpointof handleability, the method of mixing a solution of the triazinering-containing hyperbranched polymer into a dispersion of the inorganicfine particles is preferred.

The stability of the final hybridized varnish should be such as to notgive rise to any of the following: precipitation due to a decrease indispersibility, a broad change in the primary particle size or secondaryparticle size, worsening of the coating properties, discoloration(whitening, yellowing), and worsening of the film quality.

The solvent used when hybridizing the triazine ring-containinghyperbranched polymer with the inorganic fine particles is not subjectto any particular limitation, so long as the stability of the finalvarnish is not lost. In cases where a hyperbranched polymer solution andan inorganic fine particle dispersion are used to prepare thecomposition, the solvents used in each may be the same or may differ.However, to prevent a loss in stability, it is preferable for thesolvents to be close in polarity. It is not desirable to use a solventwhich clearly lowers the dispersibility of the Inorganic fine particledispersion.

Illustrative examples of solvents which may be used include toluene,p-xylene, o-xylene, m-xylene, ethylbenzene, styrene, ethylene glycoldimethyl ether, propylene glycol monomethyl ether, ethylene glycolmonomethyl ether, propylene glycol, propylene glycol monoethyl ether,ethylene glycol monoethyl ether, ethylene glycol monoisopropyl ether,ethylene glycol methyl ether acetate, propylene glycol monomethyl etheracetate, ethylene glycol ethyl ether acetate, diethylene glycol dimethylether, propylene glycol monobutyl ether, ethylene glycol monobutylether, diethylene glycol diethyl ether, dipropylene glycol monomethylether, diethylene glycol monomethyl ether, dipropylene glycol monoethylether, diethylene glycol monoethyl ether, triethylene glycol dimethylether, diethylene glycol monoethyl ether acetate, diethylene glycol,1-octanol, ethylene glycol, hexylene glycol, trimethylene glycol,1-methoxy-2-butanol, cyclohexanol, diacetone alcohol, furfuryl alcohol,tetrahydrofurfuryl alcohol, propylene glycol, benzyl alcohol,1,3-butanediol, 1,4-butanediol, 2,3-butanediol, γ-butyrolactone,acetone, methyl ethyl ketone, methyl isopropyl ketone, diethyl ketone,methyl isobutyl ketone, methyl n-butyl ketone, cyclohexanone, ethylacetate, isopropyl acetate, n-propyl acetate, isobutyl acetate, n-butylacetate, ethyl lactate, methanol, ethanol, isopropanol, tert-butanol,allyl alcohol, n-propanol, 2-methyl-2-butanol, isobutanol, n-butanol,2-methyl-1-butanol, 1-pentanol, 2-methyl-1-pentanol, 2-ethylhexanol,1-methoxy-2-propanol, tetrahydrofuran, 1,4-dioxane,N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone,1,3-dimethyl-2-imidazolidinone, dimethylsulfoxide andN-cyclohexyl-2-pyrrolidinone. These may be used singly as two or moremay be used in combination.

The content of inorganic fine particles in the composition should bewithin a range that does not compromise the dispersibility of the finalvarnish that is obtained, and may be controlled in accordance with thetarget refractive index, transmittance and heat resistance of the filmto be produced.

For example, when the amount (solids basis) of the triazinering-containing hyperbranched polymer is set to 100 parts by weight, theinorganic fine particles may be added in the range of from 0.1 to 1,000parts by weight, and preferably from 1 to 500 parts by weight. Tomaintain the film quality and obtain a stable refractive index, additionin an amount of from 10 to 300 parts by weight is more preferred.

When hybridizing the triazine ring-containing hyperbranched polymer andthe dispersion of inorganic fine particles, the subsequently describedsurfactants and other ingredients such as antisettling agents andemulsifiers may be added in order to increase the dispersibility or toincrease the compatibility.

Aside from a triazine ring-containing hyperbranched polymer, inorganicfine particles and a solvent, the film-forming composition of theinvention may include also other ingredients, such as a leveling agent,a surfactant and a crosslinking agent, provided this does not interferewith the advantageous effects of the invention.

Illustrative examples of surfactants include the following nonionicsurfactants: polyoxyethylene alkyl ethers such as polyoxyethylene laurylether, polyoxyethylene stearyl ether, polyoxyethylene cetyl ether andpolyoxyethylene oleyl ether; polyoxyethylene alkylaryl ethers such aspolyoxyethylene octylphenol ether and polyoxyethylene nonylphenyl ether;polyoxyethylene-polyoxypropylene block copolymers; sorbitan fatty acidesters such as sorbitan monolaurate, sorbitan monopalmitate, sorbitanmonostearate, sorbitan monooleate, sorbitan trioleate and sorbitantristearate; and polyoxyethylene sorbitan fatty acid esters such aspolyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitanmonopalmitate, polyoxyethylene sorbitan monostearate, polyoxyethylenesorbitan trioleate and polyoxyethylene sorbitan tristearate; andadditionally include fluorosurfactants such as those available under thetrade names Eftop EF301, EF303 and EF352 (from Mitsubishi MaterialsElectronic Chemicals Co., Ltd. (formerly Jemco Inc.)), Megafac F171,F173, R-08 and R-30 (DIC Corporation), Fluorad FC430 and FC431 (Sumitomo3M, Ltd.), AsahiGuard AG710 and Surflon S-382, SC101, SC102, SC103,SC104, SC105 and SC106 (Asahi Glass Co., Ltd.); and also theorganosiloxane polymers KP341 (Shin-Etsu Chemical Co., Ltd.) andBYK-302, BYK-307, BYK-322, BYK-323, BYK-330, BYK-333, BYK-370, BYK-375and BYK-378 (BYK-Chemie Japan KK).

These surfactants may be used singly or two or more may be used incombination. The amount of surfactant used per 100 parts by weight ofthe hyperbranched polymer is preferably from 0.0001 to 5 parts byweight, more preferably from 0.001 to 1 part by weight, and even morepreferably from 0.01 to 0.5 part by weight.

The crosslinking agent is not particularly limited, provided it is acompound having a substituent capable of reacting with the hyperbranchedpolymer of the invention.

Such compounds are exemplified by melamine compounds having acrosslink-forming substituent such as a methylol group or amethoxymethyl group, substituted urea compounds, compounds containing acrosslink-forming substituent such as an epoxy group or an oxetanegroup, compounds containing a blocked isocyanate group, compounds havingan acid anhydride group, compounds having a (meth)acryl group, andphenoplast compounds. From the standpoint of heat resistance and storagestability, a compound containing an epoxy group, a blocked isocyanategroup or a (meth)acryl group is preferred.

A blocked isocyanate group is also preferred in that, because itcrosslinks by forming a urea linkage and has a carbonyl group, therefractive index does not decrease.

When used in the treatment of polymer chain ends, it suffices for thesecompounds to have at least one crosslink-forming substituent; however,when used in cross linking treatment between polymers, they must have atleast two crosslink-forming substituents.

The epoxy compound has at least two epoxy groups on the molecule. Uponexposure of this compound to an elevated temperature during heat curing,the epoxy rings open and the crosslinking reaction proceeds via anaddition reaction with the hyperbranched polymer used in the invention.

Illustrative examples of the crosslinking agent includetris(2,3-epoxypropyl) isocyanate, 1,4-butanediol diglycidyl ether,1,2-epoxy-4-(epoxyethyl)cyclohexane, glycerol triglycidyl ether,diethylene glycol diglycidyl ether, 2,6-diglycidylphenyl glycidyl ether,1,1,3-tris[p-(2,3-epoxypropoxy)phenyl]propane,1,2-cyclohexanedicarboxylic acid diglycidyl ester,4,4′-methylenebis(N,N-diglycidylaniline),3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate,trimethylolethane triglycidyl ether, bisphenol A diglycidyl ether andpentaerythritol polyglycidyl ether.

Examples of commercial products that may be used include epoxy resinshaving at least two epoxy groups, such as YH-434 and YH-434L (from TohtoKasei Co., Ltd.); epoxy resins having a cyclohexene oxide structure,such as Epolead GT-401, GT-403, GT-301 and GT-302, and also Celloxide2021 and Celloxide 3000 (all from Daicel Chemical Industries, Ltd.);bisphenol A-type epoxy resins such as Epikote (now “jER”) 1001, 1002,1003, 1004, 1007, 1009, 1010 and 828 (all from Japan Epoxy Resin Co.,Ltd.); bisphenol F-type epoxy resins such as Epikote (now “jER”) 807(Japan Epoxy Resin Co., Ltd.); phenol-novolak type epoxy resins such asEpikote (now “jER”) 152 and 154 (Japan Epoxy Resin Co., Ltd.), and EPPN201 and 202 (Nippon Kayaku Co., Ltd.); cresol-novolak type epoxy resinssuch as EOCN-102, EOCN-103S, EOCN-104S, EOCN-1020, EOCN-1025 andEOCN-1027 (Nippon Kayaku Co., Ltd.), and Epikote (now “jER”) 180S75(Japan Epoxy Resin Co., Ltd.); alicyclic epoxy resins such as DenacolEX-252 (Nagase ChemteX Corporation), CY175, CY177 and CY179 (Ciba-GeigyAG), Araldite CY-182, CY-192 and CY-184 (Ciba-Geigy AG), Epiclon 200 and400 (DIC Corporation), Epikote (now “jER”) 871 and 872 (Japan EpoxyResin Co., Ltd.), and ED-5661 and ED-5662 (Celanese Coating KK); andaliphatic polyglycidyl ethers such as Denacol EX-611, EX-612, EX-614,EX-622, EX-411, EX-512, EX-522, EX-421, EX-313, EX-314 and EX-321(Nagase ChemteX Corporation).

The acid anhydride compound is a carboxylic acid anhydride obtained bycarrying out a dehydration/condensation reaction between two carboxylicacid molecules. Upon exposure to an elevated temperature during heatcuring, the anhydride ring opens and the crosslinking reaction proceedsby way of an addition reaction with the hyperbranched polymer used inthis invention.

Illustrative examples of the acid anhydride compound include compoundshaving a single acid anhydride group on the molecule, such as phthalicanhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride,methyl tetrahydrophthalic anhydride, methyl hexahydrophthalic anhydride,nadic anhydride, methyl nadic anhydride, maleic anhydride, succinicanhydride, octyl succinic anhydride and dodecenyl succinic anhydride;and compounds having two acid anhydride groups on the molecule, such as1,2,3,4-cyclobutanetetracarboxylic dianhydride, pyromellitic anhydride,3,4-dicarboxy-1,2,3,4-tetrahydro-1-naphthalenesuccinic dianhydride,bicyclo[3.3.0]octane-2,4,6,8-tetracarboxylic dianhydride,5-(2,5-dioxotetrahydro-3-furanyl)-3-methyl-3-cyclohexene-1,2-dicarboxylicanhydride, 1,2,3,4-butanetetracarboxylic dianhydride,3,3′,4,4′-benzophenonetetracarboxylic dianhydride,3,3′,4,4′-biphenyltetracarboxylic dianhydride,2,2-bis(3,4-dicarboxyphenyl)hexafluoropropane dianhydride and1,3-dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride.

The (meth)acrylic compound is a compound having two or more (meth)acrylgroups on the molecule. Upon exposure to an elevated temperature duringheat curing, the crosslinking reaction proceeds by way of an additionreaction with the hyperbranched polymer used in the invention.

Illustrative examples of the compound having (meth)acryl groups includeethylene glycol diacrylate, ethylene glycol dimethacrylate, polyethyleneglycol diacrylate, polyethylene glycol dimethacrylate, ethoxylatedbisphenol A diacrylate, ethoxylated bisphenol A dimethacrylate,ethoxylated trimethylolpropane triacrylate, ethoxylatedtrimethylolpropane trimethacrylate, ethoxylated glycerol triacrylate,ethoxylated glycerol trimethacrylate, ethoxylated pentaerythritoltetraacrylate, ethoxylated pentaerythritol tetramethacrylate,ethoxylated dipentaerythritol hexaacrylate, polyglycerol monoethyleneoxide polyacrylate, polyglycerol polyethylene glycol polyacrylate,dipentaerythritol hexaacrylate, dipentaerythritol hexamethacrylate,neopentyl glycol diacrylate, neopentyl glycol dimethacrylate,pentaerythritol, triacrylate, pentaerythritol trimethacrylate,trimethylolpropane triacrylate, trimethylolpropane trimethacrylate,tricyclodecane dimethanol diacrylate, tricyclodecane dimethanoldimethacrylate, 1,6-hexanediol diacrylate and 1,6-hexanedioldimethacrylate.

The above compound having (meth)acryl groups may be acquired as acommercial product, illustrative examples of which include NK EsterA-200, A-400, A-600, A-1000, A-TMPT, UA-53H, 1G, 2G, 3G, 4G, 9G, 14G,23G, ABE-300, A-BPE-4, A-BPE-6, A-BPE-10, A-BPE-20, A-BPE-30, BPE-80N,BPE-100N, BPE-200, BPE-500, BPE-900, BPE-1300N, A-GLY-3E, A-GLY-9E,A-GLY-20E, A-TMPT-3EO, A-TMPT-9EO, ATM-4E and ATM-35E (all fromShin-Nakamura Chemical Co., Ltd.); KAYARAD™ DPEA-12, PEG400DA, THE-330and RP-1040 (all from Nippon Kayaku Co., Ltd.); M-210 and M-350 (fromToagosei Co., Ltd.); KAYARAD™ DPHA, NPGDA and PET30 (Nippon Kayaku Co.,Ltd.); and NK Ester A-DPH, A-TMPT, A-DCP, A-HD-N, TMPT, DCP, NPG andHD-N (all from Shin-Nakamura Chemical Co., Ltd.).

The compound containing blocked isocyanate groups is a compound havingon the molecule at least two blocked isocyanate groups, i.e., isocyanategroups (—NCO) that have been blocked with, a suitable protecting group,and in which, upon exposure of the compound to an elevated temperatureduring heat curing, the protecting groups (blocking moieties) areremoved by thermal dissociation and the isocyanate groups that form as aresult induce crosslinking reactions with the resin. This compound isexemplified by compounds having on the molecule at least two groups ofthe following formula (which groups may be the same or may each differ).

In the formula, R_(b) is an organic group on the blocking moiety.

Such a compound can be obtained, by, for example, reacting a suitableblocking agent with a compound having at least two isocyanate groups onthe molecule.

Illustrative examples of compounds having at least two isocyanate groupson the molecule include polyisocyanates such as isophorone diisocyanate,1,6-hexamethylene diisocyanate, methylenebis(4-cyclohexyl isocyanate)and trimethylhexamethylene diisocyanate, and also dimers and trimersthereof, as well as the reaction products of these with diols, triols,diamines or triamines.

Illustrative examples of the blocking agent include alcohols such asmethanol, ethanol, isopropanol, n-butanol, 2-ethoxyhexanol,2-N,N-dimethylaminoethanol, 2-ethoxyethanol and cyclohexanol; phenolssuch as phenol, o-nitrophenol, p-chlorophenol, and o-, m- or p-cresol;lactams such as ε-caprolactam; oximes such as acetone oxime, methylethyl ketone oxime, methyl isobutyl ketone oxime, cyclohexanone oxime,acetophenone oxime and benzophenone oxime; pyrazoles such as pyrazole,3,5-dimethylpyrazole and 3-methylpyrazole; and thiols such asdodecanethiol and benzenethiol.

The compound containing blocked isocyanates may also be acquired as acommercial product, illustrative examples of which include B-830,B-815N, B-842N, B-870N, B-874N, B-882N, B-7005, B7030, B-7075 and B-5010(all from Mitsui Chemicals Polyurethane, Inc.); Duranate™ 17B-60PX,TPA-B80E, MF-B60X, MF-K60X and E402-B80T (all from Asahi Kasei ChemicalsCorporation); and KarenzMOI-BM™ (Showa Denko KK).

Aminoplast compounds are compounds which have at least twomethoxymethylene groups on the molecule. Upon exposure to an elevatedtemperature during heat curing, crosslinking reactions proceed by way ofdemethanolization/condensation reactions with the hyperbranched polymerused in the invention.

Illustrative examples of melamine compounds include the Cymel series,such as hexamethoxymethylmelamine (Cymel™ 303),tetrabutoxymethylglycoluril (Cymel™ 1170) andtetramethoxymethylbenzoguanamine (Cymel™ 1123) (all from Nihon CytecIndustries, Inc.); and the Nikalac™ series, including the methylatedmelamine resins Nikalac™ MW-30HM, MW-390, MW-100LM and MX-750LM, and themethylated urea resins Nikalac™ MX-270, MX-280 and MX-290 (all fromSanwa Chemical Co., Ltd.).

Oxetane compounds are compounds which have at least two oxetanyl groupson the molecule. Upon exposure to an elevated temperature during heatcuring, crosslinking reactions proceed by way of addition reactions withthe hyperbranched polymer used in the invention.

Examples of compounds having oxetane groups include the oxetanegroup-bearing compounds OXT-221, OX-SQ-H and OX-SC (from Toagosei Co.,Ltd.).

Phenoplast compounds are compounds which have at least twohydroxymethylene groups on the molecule. Upon exposure to an elevatedtemperature during heat curing, crosslinking reactions proceed by way ofdehydration/condensation reactions with the hyperbranched polymer usedin the invention.

Illustrative examples of phenoplast compounds include2,6-dihydroxymethyl-4-methylphenol, 2,4-dihydroxymethyl-6-methylphenol,bis(2-hydroxy-3-hydroxymethyl-5-methylphenyl)methane,bis(4-hydroxy-3-hydroxymethyl-5-methylphenyl)methane,2,2-bis(4-hydroxy-3,5-dihydroxymethylphenyl)propane,bis(3-formyl-4-hydroxyphenyl)methane,bis(4-hydroxy-2,5-dimethylphenyl)fomrylmethane andα,α-bis(4-hydroxy-2,5-dimethylphenyl)-4-formyltoluene.

The phenoplast compound may also be acquired as a commercial product,illustrative examples of which include 26DMPC, 46DMOC, DM-BIPC-F,DM-BIOC-F, TM-BIP-A, BISA-F, BI25X-DF and BI25X-TPA (all from AsahiOrganic Chemicals Industry Co., Ltd.).

These crosslinking agents may be used singly or two or more may be usedin combination. The amount of crosslinking agent used per 100 parts byweight of the hyperbranched polymer is preferably from 1 to 100 parts byweight. From the standpoint of the solvent resistance, the lower limitis preferably 10 parts by weight, and more preferably 20 parts byweight. From the standpoint of control of the refractive index, theupper limit is preferably 50 parts by weight, and more preferably 30parts by weight.

When a crosslinking agent is used, the crosslinking agent reacts withreactive end-group substituents on the hyperbranched polymer, which maymake it possible to achieve such advantageous effects as increasing thefilm density, increasing the heat resistance and increasing the thermalrelaxation properties.

Ingredients other than the above may also be added in any step duringpreparation of the inventive composition.

The film-forming composition of the invention, by being applied onto abase material and subsequently heated where necessary, is able to form adesired film.

Any suitable method may be used for applying the composition, such asspin coating, dipping, flow coating, inkjet printing, spraying, barcoating, gravure coating, slit coating, roll coating, transfer printing,brush coating, blade coating and air knife coating.

Illustrative examples of the base material include silicon, indium-tinoxide (ITO)-coated glass, indium zinc oxide (IZO)-coated glass,polyethylene terephthalate (PET), plastic, glass, quartz and ceramic.Use can also be made of a flexible base material having pliability.

The temperature at which baking is carried out in order to evaporate thesolvent is not subject to any particular limitation. For example, bakingmay be carried out at between 40 and 400° C. In such cases, to achievemore uniform film formability or to induce the reaction to proceed onthe base material, temperature change may be carried out in two or morestages.

The baking process is not particularly limited. For example, solventevaporation may be effected using a hot plate or an oven, and under asuitable atmosphere, such as in open air, in nitrogen or another inertgas, or in a vacuum.

As for the bake temperature and time, conditions which are compatiblewith the processing steps for the target electronic device should beselected. Bake conditions such that the physical values of the resultingfilm conform to the required characteristics of the electronic deviceshould be selected.

Because the film made of the inventive composition that has beenobtained in this way is able to achieve a high heat resistance, hightransparency, high refractive index, high solubility and low volumeshrinkage, it can be advantageously used as a component in thefabrication of electronic devices such as liquid-crystal displays,organic electroluminescent (EL) displays, optical semiconductor (LED)devices, solid-state image sensors, organic thin-film solar cells,dye-sensitized solar cells and organic thin-film transistors (TFT).

Where necessary, other resins (thermoplastic resins or thermoset resins)may be included in the inventive composition.

Illustrative, non-limiting, examples of such other resins include thefollowing thermoplastic resins: polyolefin resins such as polyethylene(PE), polypropylene (PP), ethylene-vinyl acetate copolymers (EVA), andethylene-ethyl acrylate copolymers (EEA); polystyrene resins such aspolystyrene (PS), high-impact polystyrene (HIPS), acrylonitrile-styrenecopolymers (AS), acrylonitrile-butadiene-styrene copolymers (ABS) andmethyl methacrylate-styrene copolymers (MS); polycarbonate resins; vinylchloride resins; polyamide resins; polyimide resins; (meth)acrylicresins such as polymethyl methacrylate (PMMA); polyester resins such aspolyethylene terephthalate (PET), polybutylene terephthalate,polyethylene naphthalate, polybutylene naphthalate, polylactic acid(PLA), poly-3-hydroxybutyric acid, polycaprolactone, polybutylenesuccinate and polyethylene succinate/adipate; polyphenylene etherresins; modified polyphenylene ether resins; polyacetal resins;polysulfone resins; polyphenylene sulfide resins; polyvinyl alcoholresins; polyglycolic acid; modified starch; cellulose acetate andcellulose triacetate; chitin and chitosan; and lignin. Other exemplaryresins include also thermoset resins such as phenolic resins, urearesins, melamine resins, unsaturated polyester resins, polyurethaneresins and epoxy resins.

These resins may be used singly or two or more may be used incombination. The amount in which such resins are used per 100 parts byweight of the hyperbranched polymer is preferably from 1 to 10,000 partsby weight, and more preferably from 1 to 1,000 parts by weight.

For example, a composition with a (meth)acrylic resin may be obtained byincluding a (meth)acrylate compound in the composition and polymerizingthe (meth)acrylate compound.

Illustrative examples of (meth)acrylate compounds include methyl(meth)acrylate, ethyl (meth)acrylate, ethylene glycol di(meth)acrylate,tetraethylene glycol di(meth)acrylate, polyethylene glycoldi(meth)acrylate, propylene glycol di(meth)acrylate, polypropyleneglycol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexanedioldi(meth)acrylate, neopentylglycol di(meth)acrylate, trimethylolpropanetrioxyethyl (meth)acrylate, tricyclodecane dimethanol di(meth)acrylate,tricyclodecanyl di(meth)acrylate, trimethylolpropane trioxypropyl(meth)acrylate, tris-2-hydroxyethyl isocyanurate tri(meth)acrylate,tris-2-hydroxyethyl isocyanurate di(meth)acrylate, 1,9-nonanedioldi(meth)acrylate, pentaerythritol di(meth)acrylate, glycerolmethacrylate acrylate, pentaerythritol tri(meth)acrylate,trimethylolpropane trimethacrylate, allyl (meth)acrylate, vinyl(meth)acrylate, epoxy (meth)acrylate, polyester (meth)acrylate andurethane (meth)acrylate.

The polymerization of these (meth)acrylate compounds may be carried outby light irradiation or heating in the presence of a photoradicalinitiator or a thermal radical initiator.

Examples of photoradical initiators include acetophenones,benzophenones, Michler's benzoyl benzoate, amyloxime ester,tetramethylthiuram monosulfide and thioxanthones.

Photocleavable photoradical initiators are especially preferred.Photocleavable photoradical initiators are listed on page 159 of SaishinUV Kōka Gijutsu [Recent UV Curing Technology] (publisher, K. Takansu;published by Gijutsu Joho Kyokai KK; 1991).

Examples of commercial photoradical initiators include those availablefrom BASF under the trade names Irgacure 184, 369, 651, 500, 819, 907,784 and 2959, the trade names CGI1700, CGI1750, CGI1850 and CG24-61, thetrade names Darocur 1116 and 1173, and the trade name Lucirin TPO; thatavailable from UCB under the trade name Ubecryl P36; and those availableunder the trade names Esacure KIP150, KIP65LT, KIP100F, KT37, KT55,KTO46 and KIP75/B from the Fratelli Lamberti Company.

The photoradical initiator is used in the range of preferably from 0.1to 15 parts by weight, and more preferably from 1 to 10 parts by weight,per 100 parts by weight of the (meth)acrylate compound.

The solvent used in polymerization is exemplified by the same solventsas those mentioned above for the film-forming composition.

EXAMPLES

The invention is illustrated more fully below by way of Working Examplesof the invention and Comparative Examples, although the invention is notlimited by these Examples. The instruments used for measurement in theExamples were as follows.

¹H-NMR

-   -   Instruments: Varian NMR System 400 NB (400 MHz)        -   JEOL-ECA700 (700 MHz)    -   Solvent used in measurement: DMSO-d6    -   Reference material: Tetramethylsilane (TMS) (δ=0.0 ppm)        GPC    -   Instrument HLC-8200 GPC (Tosoh Corporation)    -   Columns: Shodex KF-804L+KF-805L    -   Column temperature: 40° C.    -   Solvent: Tetrahydrofuran (THF)    -   Detector: UV (254 nm)    -   Calibration curve: polystyrene standard        Ultraviolet-Visible Spectrophotometer    -   Instrument: Shimadzu UV-3600 (Shimadzu Corporation)        Ellipsometer    -   Instrument: VASE multiple incident angle spectroscopic        ellipsometer (JA Woollam Japan)        Transmission Electron Microscope    -   Instrument: JEM-1010 (JEOL Ltd.)

[1] Synthesis of Hyperbranched Polymer Synthesis Example 1 Synthesis ofTriazine Ring-Containing Hyperbranched Polymer [3]

Under an air atmosphere, 28.94 g of m-phenylenediamine [2] (0.27 mol,Aldrich) was added to a 1,000 mL four-neck flask, dissolved in 121 mL ofN,N-dimethylacetamide (DMAc), and heated to 100° C. on an oil bath.Next, 36.91 g of 2,4,6-trichloro-1,3,5-triazine [1] (0.20 mol; TokyoChemical Industry) dissolved in 261.5 mL of DMAc was added andpolymerization was started.

After 50 minutes, 56.53 g of aniline (0.6 mol; Junsei Chemical Co.,Ltd.) was added and the flask contents were stirred for 1 hour, stoppingpolymerization. The reaction mixture was allowed to cool to roomtemperature, then was reprecipitated in a mixed solution of 28% ammoniawater (30.4 g) dissolved in 1,600 mL of water and 520 mL of methanol.The precipitate was collected by filtration, re-dissolved in 400 mL ofTHF and 15 mL of N,N-dimethylformamide, then reprecipitated in 2,100 mLof ion-exchanged water. The resulting precipitate was collected byfiltration and dried in a vacuum desiccator at 150° C. for 6 hours,yielding 49.78 g of the target polymeric compound [3] (abbreviated belowas “HB-TmDA45”). FIG. 1 shows the measured ¹H-NMR spectrum forHB-TmDA45. The HB-TmDA45 thus obtained was a compound having structuralunits of formula (24). The polystyrene-equivalent weight-averagemolecular weight Mw of HB-TmDA45, as measured by GPC, was 4,600, and thepolydispersity Mw/Mn was 2.37.

An amount of 1.0 g of the HB-TmDA45 thus obtained was dissolved in 9.0 gof cyclohexanone (CHN), giving a clear, light yellow-colored solution.Using a spin coater, the resulting polymer varnish was spin-coated ontoa glass substrate for 5 seconds at 200 rpm and for 30 seconds at 2,000rpm, following which the solvent was removed by a 2-minute bake at 150°C. and a 5-minute bake at 250° C., thereby forming a film. The resultingfilm had a refractive index at 550 nm of 1.8030.

The following titania dispersions (1) to (3) were used in the examplesdescribed below.

-   Titania Dispersion (1): A 1-methoxy-2-propanol dispersion containing    10.5 wt % of colloidal particles of anatase-type titania (primary    particle size, 6 to 10 nm).-   Titania Dispersion (2): A 1-methoxy-2-propanol dispersion containing    10.5 wt % of colloidal particles of rutile-type titania (primary    particle size, 6 to 10 nm).-   Titania Dispersion (3): A 1-methoxy-2-propanol dispersion containing    20.5 wt % of colloidal particles (primary particle size, 6 to 10 nm)    of a complex oxide of titanium oxide, zirconium oxide and tin oxide    (TiO₂:ZrO₂:SnO₂=1:0.2:0.1, by weight).

[2] Production of Film-Forming Composition and Film Example 1

A 20% CNH solution of HB-TmDA45 was prepared by weighing out 2.0000 g ofthe HB-TmDA45 obtained in Synthesis Example 1 into a 20 mL pear-shapedflask, then adding 10.0000 g of CHN and effecting complete dissolutionat room temperature.

A varnish (abbreviated below as “HB1-100”) having a total solids contentof 8.0 wt % was obtained by weighing out 2.0000 g of the 20% CHNsolution of HB-TmDA45 prepared above into a 20 mL pear-shaped flask,adding 3.8095 g of Titania Dispersion (1) (the solids content of theinorganic fine particles, relative to the solids content of theHB-TmDA45, being 100 parts by weight), adding 0.0400 g of a solutionobtained by diluting BYK-307 (BYK-Chemie Japan KK) as the surfactantwith 1-methoxy-2-propanol (PGME) to a concentration by weight of 0.1%,then adding 4.1555 g of PGME and mixing to complete uniformity at roomtemperature.

Using a spin coater, the resulting HB1-100 varnish was spin-coated ontosilicon substrates or quartz substrates for 30 seconds at 3,000 rpm.Next, using a hot plate, the respective varnish-coated substrates weresubjected to, respectively: A) a 1-minute bake at 100° C., B) a 1-minutebake at 100° C. followed by a 5-minute bake at 200° C., C) a 1-minutebake at 100° C. followed by a 5-minute bake at 250° C., or D) a 1-minutebake at 100° C. followed by a 5-minute bake at 300° C., thereby formingfilms.

Example 2

A varnish (abbreviated below as “HB1-200”) having a total solids contentof 8.0 wt % was obtained by weighing out 1.5000 g of a 20% CHN solutionof HB-TmDA45 prepared in the same way as in Example 1 into a 20 mLpear-shaped flask, adding 5.7143 g of Titania Dispersion (1) (the solidscontent of the inorganic fine particles, relative to the solids contentof the HB-TmDA45, being 200 parts by weight), adding 0.0300 g of asolution obtained by diluting BYK-307 (BYK-Chemie Japan KK) as thesurfactant with PGME to a concentration by weight of 0.1%, then adding4.0095 g of PGME and mixing to complete uniformity at room temperature.

Aside from using the HB1-200 varnish thus obtained, the varnish wasspin-coated onto silicon substrates or quartz substrates in the same wayas in Example 1, following which baking was carried out under the samerespective conditions A), B), C) and D) as in Example 1, thereby formingfilms.

Example 3

A varnish (abbreviated below as “HB1-300”) having a total solids contentof 8.0 wt % was obtained by weighing out 1.0000 g of a 20% CHN solutionof HB-TmDA45 prepared in the same way as in Example 1 into a 20 mLpear-shaped flask, adding 5.7143 g of Titania Dispersion (1) (the solidscontent of the inorganic fine particles, relative to the solids contentof the HB-TmDA45, being 300 parts by weight), adding 0.0200 g of asolution, obtained by diluting BYK-307 (BYK-Chemie Japan KK) as thesurfactant with PGME to a concentration by weight of 0.1%, then adding3.2682 g of PGME and mixing to complete uniformity at room temperature.

Aside from using the HB1-300 varnish thus obtained, the varnish wasspin-coated onto silicon substrates or quartz substrates in the same wayas in Example 1, following which baking was carried out under the samerespective conditions A), B), C) and D) as in Example 1, thereby formingfilms.

Example 4

A varnish (abbreviated below as “HB2-100”) having a total solids contentof 8.0 wt % was obtained by weighing out 2.0000 g of a 20% CHN solutionof HB-TmDA45 prepared in the same way as in Example 1 into a 20 mLpear-shaped flask, adding 3.8095 g of Titania Dispersion (2) (the solidscontent of the inorganic fine particles, relative to the solids contentof the HB-TmDA45, being 100 parts by weight), adding 0.0400 g of asolution obtained by diluting BYK-307 (BYK-Chemie Japan KK) as thesurfactant with PGME to a concentration by weight of 0.1%, then adding4.1555 g of PGME and mixing to complete uniformity at room temperature.

Aside from using the HB2-100 varnish thus obtained, the varnish wasspin-coated onto silicon substrates or quartz substrates in the same wayas in Example 1, following which baking was carried out under the samerespective conditions A), B), C) and D) as in Example 1, thereby formingfilms.

Example 5

A varnish (abbreviated below as “HB2-200”) having a total solids contentof 8.0 wt % was obtained by weighing out 1.5000 g of a 20% CHN solutionof HB-TmDA45 prepared in the same way as in Example 1 into a 20 mLpear-shaped flask, adding 5.7143 g of Titania Dispersion (2) (the solidscontent of the inorganic fine particles, relative to the solids contentof the HB-TmDA45, being 200 parts by weight), adding 0.0300 g of asolution obtained by diluting BYK-307 (BYK-Chemie Japan KK) as thesurfactant with PGME to a concentration by weight of 0.1%, then adding4.0095 g of PGME and mixing to complete uniformity at room temperature.

Aside from using the HB2-200 varnish thus obtained, the varnish wasspin-coated onto silicon substrates or quartz substrates in the same wayas in Example 1, following which baking was carried out under the samerespective conditions A), B), C) and D) as in Example 1, thereby formingfilms.

Example 6

A varnish (abbreviated below as “HB2-300”) having a total solids contentof 8.0 wt % was obtained by weighing out 1.0000 g of a 20% CHN solutionof HB-TmDA45 prepared in the same way as in Example 1 into a 20 mLpear-shaped flask, adding 5.7143 g of Titania Dispersion (2) (the solidscontent of the inorganic fine particles, relative to the solids contentof the HB-TmDA45, being 300 parts by weight), adding 0.0200 g of asolution obtained by diluting BYK-307 (BYK-Chemie Japan KK) as thesurfactant with PGME to a concentration by weight of 0.1%, then adding3.2682 g of PGME and mixing to complete uniformity at room temperature.

Aside from using the HB2-300 varnish thus obtained, the varnish wasspin-coated onto silicon substrates or quartz substrates in the same wayas in Example 1, following which baking was carried out under the samerespective conditions A), B), C) and D) as in Example 1, thereby formingfilms.

Example 7

A varnish (abbreviated below as “HB3-100”) having a total solids contentof 8.0 wt % was obtained by weighing out 2.0000 g of a 20% CHN solutionof HB-TmDA45 prepared in the same way as in Example 1 into a 20 mLpear-shaped flask, adding 1.9512 g of Titania Dispersion (3) (the solidscontent of the inorganic fine particles, relative to the solids contentof the HB-TmDA45, being 100 parts by weight), adding 0.0400 g of asolution obtained by diluting BYK-307 (BYK-Chemie Japan KK) as thesurfactant with PGME to a concentration by weight of 0.1%, then adding6.0138 g of PGME and mixing to complete uniformity at room temperature.

Aside from using the HB3-100 varnish thus obtained, the varnish wasspin-coated onto silicon substrates or quartz substrates in the same wayas in Example 1, following which baking was carried out under the samerespective conditions A), B), C) and D) as in Example 1, thereby formingfilms.

Example 8

A varnish (abbreviated below as “HB3-200”) having a total solids contentof 8.0 wt % was obtained by weighing out 1.5000 g of a 20% CHN solutionof HB-TmDA45 prepared in the same way as in Example 1 into a 20 mlpear-shaped flask, adding 2.9268 g of Titania Dispersion (3) (the solidscontent of the inorganic fine particles, relative to the solids contentof the HB-TmDA45, being 200 parts by weight), adding 0.0300 g of asolution obtained by diluting BYK-307 (BYK-Chemie Japan KK) as thesurfactant with PGME to a concentration by weight of 0.1%, then adding6.7969 g of PGME and mixing to complete uniformity at room temperature.

Aside from using the HB3-200 varnish thus obtained, the varnish wasspin-coated onto silicon substrates or quartz substrates in the same wayas in Example 1, following which baking was carried out under the samerespective conditions A), B), C) and D) as in Example 1, thereby formingfilms.

Example 9

A varnish (abbreviated below as “HB3-300”) having a total solids contentof 8.0 wt % was obtained by weighing out 1.0000 g of a 20% CHN solutionof HB-TmDA45 prepared in the same way as in Example 1 into a 20 mLpear-shaped flask, adding 2.9268 g of Titania Dispersion (3) (the solidscontent of the inorganic fine particles, relative to the solids contentof the HB-TmDA45, being 300 parts by weight), adding 0.0200 g of asolution obtained by diluting BYK-307 (BYK-Chemie Japan KK) as thesurfactant with PGME to a concentration by weight of 0.1%, then adding6.0557 g of PGME and mixing to complete uniformity at room temperature.

Aside from using the HB3-300 varnish thus obtained, the varnish wasspin-coated onto silicon substrates or quartz substrates in the same wayas in Example 1, following which baking was carried out under the samerespective conditions A), B), C) and D) as in Example 1, thereby formingfilms.

Comparative Example 1

A varnish (abbreviated below as “PSQ1-300”) having a total solidscontent of 8.0 wt % was obtained by weighing out 0.5000 g of a solutionof phenysilsesquioxane (abbreviated below as “PSQ”; from Gelest, Inc.)diluted with PGME to a concentration of 60 wt % into a 20 mL pear-shapedflask, adding 8.5714 g of Titania Dispersion (1) (the solids content ofthe inorganic fine particles, relative to the solids content of the PSQ,being 300 parts by weight), adding 0.0300 g of a solution obtained bydiluting BYK-307 (BYK-Chemie Japan KK) as the surfactant with PGME to aconcentration by weight of 0.1%, then adding 5.9023 g of PGME and mixingto complete uniformity at room temperature.

Aside from using the PSQI-300 varnish thus obtained, the varnish wasspin-coated onto silicon substrates or quartz substrates in the same wayas in Example 1, following which baking was carried out under the samerespective conditions A), B), C) and D) as in Example 1, thereby formingfilms.

Comparative Example 2

A varnish (abbreviated below as “PSQ2-300”) having a total solidscontent of 8.0 wt % was obtained by weighing out 0.5000 g of a solutionof PSQ (Gelest, Inc.) diluted with PGME to a concentration of 60 wt %into a 20 mL pear-shaped flask, adding 8.5714 g of Titania Dispersion(2) (the solids content of the inorganic fine particles, relative to thesolids content of the PSQ, being 300 parts by weight), adding 0.0300 gof a solution obtained by diluting BYK-307 (BYK-Chemie Japan KK) as thesurfactant with PGME to a concentration by weight of 0.1%, then adding5.9023 g of PGME and mixing to complete uniformity at room temperature.

Aside from using the PSQ2-300 varnish thus obtained, the varnish wasspin-coated onto silicon substrates or quartz substrates in the same wayas in Example 1, following which baking was carried out under the samerespective conditions A), B), C) and D) as in Example 1, thereby formingfilms.

Comparative Example 3

A varnish (abbreviated below as “PSQ3-300”) having a total solidscontent of 8.0 wt % was obtained by weighing out 0.5000 g of a solutionof PSQ (Gelest, Inc.) diluted with PGME to a concentration of 60 wt %into a 20 mL pear-shaped flask, adding 4.3902 g of Titania Dispersion(3) (the solids content of the inorganic fine particles, relative to thesolids content of the PSQ, being 300 parts by weight), adding 0.0300 gof a solution obtained by diluting BYK-307 (BYK-Chemie Japan KK) as thesurfactant with PGME to a concentration by weight of 0.1%, then adding10.0835 g of PGME and mixing to complete uniformity at room temperature.Aside from using the PSQ3-300 varnish thus obtained, the varnish wasspin-coated onto silicon substrates or quartz substrates in the same wayas in Example 1, following which baking was carried out under the samerespective conditions. A), B), C) and D) as in Example 1, therebyforming films.

Measurement of Refractive Index

The refractive indices at 633 nm of the films formed on siliconsubstrates under the various bake conditions in the respective workingexamples of the invention and comparative examples above were measuredwith an ellipsometer, and the thermal stabilities of the film refractiveindices were evaluated. The results are shown in Table 1.

The thermal stability of the refractive index was evaluated by comparingthe refractive indices under bake conditions B) and D) and calculatingthe refractive index difference (□) therebetween. A smaller refractiveindex difference indicates a better refractive index thermal stability.If the difference is a positive value, the refractive index obtainedunder bake conditions D) increases relative to that obtained under bakeconditions B), whereas if the difference is a negative value, therefractive index obtained under bake conditions D) decreases relative tothat obtained under bake conditions B). When this difference in therefractive indices is a negative value and the value is large, therefractive index decreases as the bake temperature rises; hence, thethermal stability of the refractive index is poor.

TABLE 1 Refractive index difference Refractive index at 633 nm (Δ) A) B)C) D) D)-B) Example 1 1.7884 1.8202 1.8250 1.8345 0.0143 Example 21.8028 1.8274 1.8364 1.8367 0.0093 Example 3 1.8163 1.8189 1.8149 1.8049−0.0140 Example 4 1.8111 1.8407 1.8456 1.8540 0.0133 Example 5 1.83291.8610 1.8745 1.8853 0.0243 Example 6 1.8573 1.8732 1.8806 1.8681−0.0051 Example 7 1.7818 1.8076 1.8088 1.8150 0.0074 Example 8 1.78741.7917 1.7854 1.7726 −0.0191 Example 9 1.7709 1.7566 1.7428 1.7321−0.0245 Comparative Example 1 1.7794 1.7637 1.7405 1.7142 −0.0495Comparative Example 2 1.8151 1.8026 1.7758 1.7526 −0.0500 ComparativeExample 3 1.7221 1.7031 1.6858 1.6662 −0.0369

As shown in Table 1, the films produced in Examples 1 to 9 exhibitedvery high refractive indices of about 1.8 at a wavelength of 633 nm, inaddition, to which the thermal stabilities of the refractive indiceswere also high.

By contrast, in Comparative Examples 1 to 3, when the bake temperaturewas raised, the refractive index of the films obtained decreased,indicating that the refractive indices of these films had a poor thermalstability.

Measurement of Transmittance

The transmittances of the films produced on silicon substrates under thevarious bake conditions in the respective working examples andcomparative examples above were measured with an ultraviolet-visiblespectrophotometer. The background when measuring the transmittance was aquartz substrate not coated with a film. The transmittance was measuredover a wavelength range of from 200 to 800 nm. The results oftransmittance measurements for the films produced in Examples 1 to 9 andComparative Examples 1 to 3 are shown respectively in FIGS. 2 to 13.

As shown in FIGS. 2 to 13, the transmittances were good values of atleast 90% in the visible light region of from 400 to 800 nm.

Moreover, even when the bake conditions were changed, a marked decreasein the transmittance did not occur. This demonstrated that theheat-resistant transmittance was good, that the temperature margin whenfabricating electronic devices is broad, and that stable films can beobtained.

Solvent Resistance

The solvent resistance test refers to a test indicating that the filmobtained after the main bake is insoluble when brought into contact witha solvent. Solvent resistance is a property that is essential when thesubsequent steps of recoating the film with a resist or the like andpatterning are additionally carried out. In the absence of solventresistance, the film will dissolve in the resist solution duringrecoating, leading to mixing of the film and the resist, as a result ofwhich the inherent properties of the film may not be achieved.

Example 10

A solvent resistance test was carried out on the film formed on asilicon substrate under condition B) in Example 3.

The film thickness after baking was 198.4 nm. This was treated as theinitial film thickness. Separate films were each independently immersedcompletely in propylene glycol monomethyl ether, propylene glycolmonomethyl ether acetate, cyclohexanone, acetone or ethyl lactate, andleft to stand 5 minutes. Next, the films were dried in air, after whichthe residual solvent was completely evaporated by a 1-minute bake on a200° C. hot plate. The film thickness was then measured and comparedwith the initial film thickness.

As a result, letting the initial thickness of the film be 100%, the filmthicknesses following immersion in the respective solvents were 100.0%for propylene glycol monomethyl ether, 100.0% for propylene glycolmonomethyl ether acetate, 100.0% for cyclohexanone, 100.0% for acetone,and 100.0% for ethyl acetate. Hence, the film was found to have goodsolvent resistances to various types of organic solvents.

Example 11

Aside from using the film formed on a silicon substrate under conditionB) in Example 6, a solvent resistance test was carried out in the sameway as in Example 10. The film thickness after baking was 195.5 nm. Thiswas treated as the initial film thickness.

Letting the initial thickness of the film be 100%, the film thicknessesfollowing immersion in the respective solvents were 100.0% for propyleneglycol monomethyl ether, 100.0% for propylene glycol monomethyl etheracetate, 100.0% for cyclohexanone, 100.0% for acetone, and 100.0% forethyl acetate. Hence, the film was found to have good solventresistances to various types of organic solvents.

Example 12

Aside from using the film formed on a silicon substrate under conditionB) in Example 9, a solvent resistance test was carried out in the sameway as in Example 10. The film thickness after baking was 194.9 nm. Thiswas treated as the initial film thickness.

Letting the initial thickness of the film be 100%, the film thicknessesfollowing immersion in the respective solvents were 100.0% for propyleneglycol monomethyl ether, 100.0% for propylene glycol monomethyl etheracetate, 100.0% for cyclohexanone, 100.0% for acetone, and 100.0% forethyl acetate. Hence, the film was found to have good solventresistances to various types of organic solvents.

Comparative Example 4

A solvent resistance test was carried out on a film formed on a siliconsubstrate without the addition of inorganic fine particles to the 20%CHN solution of HB-TmDA45 prepared in Example 1.

That is, a film was formed by spin-coating a 20% CHN solution ofHB-TmDA45 onto a silicon substrate, followed by a 1-minute bake at 100°C. and a 5-minute bake at 200° C. The film thickness after baking was500.4 nm. This was treated as the initial film thickness. Aside fromusing this film, a solvent resistance test was carried out in the sameway as in Example 10.

Letting the initial thickness of the film be 100%, the film thicknessesfollowing immersion in the respective solvents were 0.0% for propyleneglycol monomethyl ether, 0.0% for propylene glycol monomethyl etheracetate, 0.0% for cyclohexanone, 0.0% for acetone, and 0.0% for ethylacetate. Hence, the solvent resistance of the film with respect to eachof these organic solvents was poor.

Upon comparing the results from Examples 10 to 12 with the results fromComparative Example 4, it was found that solvent resistance emerges inhybrid films obtained by adding inorganic fine particles and baking.

Light Resistance Test

Light irradiation in the light resistance tests was carried out at theJapan Weathering Test Center. A xenon arc lamp having an illuminance of38.7 W/m² was used as the light source.

Example 13

A light resistance test was carried out on the film formed on a quartzsubstrate under condition D) in Example 2. The light resistance testentailed 12.5 hours of exposure to light using the above-indicated lightsource. This light irradiation is equivalent to a light exposure dose of1,000,000 lux, which is generally known to correspond to one year ofoutdoor exposure.

Example 14

A light resistance test like that in Example 13 was earned out on thefilm formed on a quartz substrate under condition D) in Example 5.

Example 15

A light resistance test like that in Example 13 was carried out on thefilm formed on a quartz substrate under condition D) in Example 8.

Table 2 shows the results obtained from measurements of the refractiveindices of the films following 1,000,000 lux of irradiation in aboveExamples 13 to 15.

TABLE 2 Refractive index at 633 nm Before light exposure After lightexposure Example 13 1,8367 1.8133 Example 14 1.8853 1.8869 Example 151.7726 1.7666

As shown in Table 2, the hybrid materials obtained in Examples 13 to 15had very good light resistances, and showed little or no decrease inrefractive index even with 1,000,000 lux of light exposure. Inparticular, the film formed in Example 14 had a good light resistance,suggesting that, among various types of titania in the form of inorganicfine particles, rutile-type titania has a superior light resistance.

As shown above, by using the inventive film-forming composition whichincludes a triazine ring-containing hyperbranched polymer and inorganicfine particles, it is possible to obtain a highly transparent film whichhas a refractive index at 633 nm of about 1.8, is resistant to changesin refractive index at bake temperatures up to 300° C., and has a goodlight resistance.

Moreover, because the film of the invention has solvent resistance,mixing does not occur when a resist or the like is recoated, thusenabling the stable use of semiconductor processes.

In addition, because the hybrid material can be stably formed into avarnish without a loss in the dispersion stability of the inorganic fineparticles, it has an excellent storage stability. Furthermore, becausethe storage stability is good, this leads to stable production andstable supply during fabrication of the target electronic device,enabling costs to be reduced and throughput to be increased in devicefabrication, and ultimately resulting in an improved production yield.

What is claimed is:
 1. A film-forming composition characterized bycomprising: inorganic fine particles; and a triazine ring-containinghyperbranched polymer which includes recurring unit structures offormula (1) below

wherein R and R′ are each independently a hydrogen atom or an alkyl,alkoxy, aryl or aralkyl group; and Ar is a divalent organic group whichincludes either of, or both, an aromatic ring and a heterocycle, whereinthe hyperbranched polymer is capped on at least one end by an alkyl,aralkyl, aryl, alkylamino, alkoxysilyl-containing alkylamino,aralkylamino, arylamino, alkoxy, aralkyloxy, aryloxy, or ester group. 2.The film-forming composition according to claim 1, wherein Ar is atleast one moiety selected from the group consisting of moieties offormulas (2) to (18) below

wherein R¹ to R¹²⁸ are each independently a hydrogen atom, a halogenatom, a carboxyl group, a sulfonyl group, an alkyl group which may havea branched structure of 1 to 10 carbons, or an alkoxy group which mayhave a branched structure of 1 to 10 carbons; W¹ and W² are eachindependently a single bond, CR¹²⁹R¹³⁰ wherein R¹²⁹ and R¹³⁰ being eachindependently a hydrogen atom or an alkyl group which may have abranched structure of 1 to 10 carbons, with the proviso that R¹²⁹ andR¹³⁰ may together form a ring, C═O, O, S, SO, SO₂ or NR¹³¹ wherein R¹³¹being a hydrogen atom or an alkyl group which may have a branchedstructure of 1 to 10 carbons; and X¹ and X² are each independently asingle bond, an alkylene group which may have a branched structure of 1to 10 carbons, or a group of formula (19) below

R¹³² to R¹³⁵ being each independently a hydrogen atom, a halogen atom, acarboxyl group, a sulfonyl group, an alkyl group which may have abranched structure of 1 to 10 carbons, or an alkoxy group which may havea branched structure of 1 to 10 carbons; and Y¹ and Y² being eachindependently a single bond or an alkylene group which may have abranched structure of 1 to 10 carbons.
 3. The film-forming compositionaccording to claim 2, wherein Ar is at least one moiety selected fromthe group consisting of moieties of formulas (5) to (12) and moieties offormulas (14) to (18).
 4. The film-forming composition according toclaim 2, wherein Ar is at least one moiety selected from the groupconsisting of moieties of formulas (20) to (22) below

wherein R³² to R³⁷, R⁶⁹ to R⁸⁰, R¹²⁹, R¹³⁰ and R¹³² to R¹³⁵ are asdefined above.
 5. The film-forming composition according to claim 1,wherein the recurring unit structure has formula (23) below


6. The film-forming composition according to claim 1, wherein therecurring unit structure has formula (24) below

wherein R and R′ are as defined above.
 7. The film-forming compositionaccording to claim 6, wherein the recurring unit structure has formula(25) below


8. The film-forming composition according to claim 1, wherein thehyperbranched polymer has at least one terminal triazine ring which iscapped by an alkyl, aralkyl, aryl, alkylamino, alkoxysilyl-containingalkylamino, aralkylamino, arylamino, alkoxy, aralkyloxy, aryloxy orester group.
 9. The film-forming composition according to claim 1,wherein the inorganic fine particles are an oxide, sulfide or nitride ofone or more metal selected from the group consisting of Be, Al, Si, Ti,V, Fe, Cu, Zn, Y, Zr, Nb, Mo, In, Sn, Sb, Ta, W, Pb, Bi and Ce.
 10. Thefilm-forming composition according to claim 9, wherein the inorganicfine particles have a primary particle size of 2 to 50 nm and arecolloidal particles of an oxide of one or more metal selected from thegroup consisting of Be, Al, Si, Ti, V, Fe, Cu, Zn, Y, Zr, Nb, Mo, In,Sn, Sb, Ta, W, Pb, Bi and Ce.
 11. The film-forming composition accordingto claim 9, wherein the inorganic fine particles are surface-treatedwith an organosilicon compound.